Process for preparing 2-oxazolidone and its derivatives

ABSTRACT

Process for preparing 2-oxazolidone and its derivatives by reacting react carbon dioxide with aziridine compound, preferably, in the presence of Lewis acid as a catalyst.

This is a continuation of application Ser. No. 779,335, filed Mar. 21,1977, now abandoned.

BACKGROUND OF THE INVENTION

2-oxazoidone and its derivatives are represented by the followingformula: ##STR1##

2-oxazolidone has the following formula: ##STR2##

A derivative of 2-oxazolidone such as 4-methyl-2-oxazolidone has thefollowing formula: ##STR3##

Such 2-oxazolidone and its derivatives are useful as intermediates inthe preparation of drugs, and polymers of 2-oxazolidone derivatives areused, for example, in preparation of fibers, tablet coatings, lubricantadditives, cigarette filters, rust inhibitors and dyeing assistants.

Many conventional processes for preparing 2-oxazolidone and itsderivatives are known. 2-oxazolidone may be prepared by the reaction asshown below:

the reaction of β-aminoalcohol with a compound selected from the groupconsisting of phosgene, dialkylcarbonate, carbon dioxide, urea,isocyanate, ethylchlorocarbonate, carbon disulfide;

the reaction of epoxide with a compound selected from the groupconsisting of cyanuric acid, urea and cyanamide;

the reaction of acrolein with isocyanate; or the removal of hydrochloricacid from β-hydroxyalkylsemicarbazide.

However, such conventional processes have disadvantages, for example,high cost of starting raw materials, complexity of the procedure or lowyield of 2-oxazolidone and its derivatives.

It is an object of the present invention to provide a process ofpreparing 2-oxazolidone and its derivatives at a low cost and a highyield.

SUMMARY OF THE INVENTION

The present invention relates to a process for preparing 2-oxazolidoneand its derivatives.

2-oxazolidone and its derivatives have the following general formula:##STR4## wherein R₁ is hydrogen, a lower alkyl group of 1 to 4 carbonatoms, phenyl and benzyl, and R₂ is hydrogen, a lower alkyl group of 1to 4 carbon atoms, a substituted lower alkyl group such as β-cyanoethyl,β-aminopropyl, α-hydroxyethyl and β-chloroethyl, unsubstituted orsubstituted phenyl, benzyl, an acyl group such as formyl, acetyl,propionyl, benzoyl, toluoyl, acryloyl and methacryloyl.

The process of the present invention comprises reacting carbon dioxidewith an aziridine compound.

Aziridine compounds include aziridine and its derivatives represented bythe following formula: ##STR5## wherein R₁ and R₂ are as hereinbeforedefined. ##STR6##

The reaction of carbon dioxide with an aziridine compound may be carriedout in a solvent. Such solvents include saturated paraffinichydrocarbons such as n-heptane, aromatic hydrocarbons such as benzane,substituted aromatic hydrocarbons such as o-dichlorobenzene,cycloparaffins such as cyclohexane, alcohols such as methanol andethanol, ethers such as diethylether, ketones such as acetone,halogenated hydrocarbons such as chloroform, cyclic esters such astetrahydrofuran, sulfoxides such as dimethyl sulfoxide, and amides suchas formamide.

The reaction of the present invention may be carried out at atemperature of 0° C. to 200° C., preferably 20° C. to 120° C., by usinga mixture of carbon dioxide and aziridine compound in the molar ratio(CO₂ /aziridines) of 0.1 to 1,000, preferably 1 to 100.

The reaction of the present invention may effectively be carried out inthe presence of Lewis acid as a catalyst.

Preferred Lewis acids used as a catalyst in the present inventioninclude halogens such as chlorine, bromine and iodine, halogenides oftitanium, aluminium, manganese, copper, tin, antimony, iron, zinc,phosphorus and boron.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The following examples are given by way of illustration only:

EXAMPLE 1

2.5 l (S.T.P.) of carbon dioxide, 3.2 g of propyleneimine, 75 mg ofiodine and 8.0 g of chloroform were placed in a stainless steelhigh-pressure tube of about 300 ml in volume. After the mixture wasallowed to react at a temperature of 30° C. for 31 hours, the reactionproduct was taken out of the high-pressure tube and distilled underreduced pressure to obtain 2.4 g of pure 4-methyl-2-oxazolidone, whichhas the properties as shown below:

b.p. 128°-130° C. (3 mmHg); n.m.r. (CDCl₃) δ 1.3(3H, CH₃, d), 4.0(1H,CH₂ and 1H, CH, m), 4.5(1H, CH₂, S) and 6.7(1H, NH, broad); i.r. ν_(max)1735 and 1240cm⁻¹ ;

    ______________________________________                                        Analysis:        C(%)     H(%)     N(%)                                       ______________________________________                                        Found            47.38    7.10     14.35                                      Calculated for C H.sub.2 NO.sub.3                                                              42.81    6.53     13.86                                      ______________________________________                                    

EXAMPLE 2

3 l (S.T.P.) of carbon dioxide, 3.2 g of ethyleneimine, 50 mg of zincchloride and 20 g of ethanol were placed in a stainless steelhigh-pressure tube of 300 ml in volume. After the mixture was allowed toreact at a temperature of 60° C. for 50 hours, the reaction product wastaken out of the high-pressure tube and recrystallized from chloroformsolution of the reaction product to obtain 1.5 g of pure 2-oxazolidone,which has the properties as shown below:

m.p. 86°-88° C.; n.m.r. (D₂ O) δ 4.14(2H, CH₂, t), 5.02(2H, CH₂, t);i.r. ν_(max) 1735, 1256, 1085, 1023, 970 and 920cm⁻¹ ;

    ______________________________________                                        Analysis:        C(%)     H(%)     N(%)                                       ______________________________________                                        Found            41.70    5.87     16.11                                      Calculated for C.sub.2 H.sub.4 NO.sub.2                                                        41.38    8.75     16.09                                      ______________________________________                                    

EXAMPLE 3-7

The same procedure as that described in Example 1 was repeated exceptthat the procedure was carried out under the conditions as shown belowto obtain pure 4-methyl-2-oxazolidone:

    __________________________________________________________________________         Carbon Propylene-                                                                          Catalyst    Reaction                                                                             Reaction                                                                           4-methyl-2-                         Example                                                                            dioxide                                                                              imine (Lewis acid)                                                                         Solvent                                                                            temperature                                                                          time oxazolidone                         No.  (l) (S.T.P.)                                                                         (g)   (mg)   (g)  (°C.)                                                                         (hcur)                                                                             (g)                                 __________________________________________________________________________                      ferric                                                      3    2.4    3.5   chloride                                                                             hexane                                                                             100    50   1.2                                                   50     20                                                   4    7      4     phosphorus                                                                           acetone                                                                            20     48   3.5                                                   trichloride                                                                          50                                                                     50                                                          5    5      3.2   antimony                                                                             benzene                                                                            75     52   3                                                     tribromide                                                                           60                                                                     60                                                          6    3      3.5   tin tetra-                                                                           --   50     48   1.5                                                   chloride                                                                      50                                                          7    5      4     --     chloro-                                                                            80     50   0.3                                                          form                                                                          30                                                   __________________________________________________________________________

EXAMPLE 8-10

The same procedure as that described in Example 2 was repeated exceptthat the procedure was carried out under the conditions as shown belowto obtain pure 2-oxazolidone:

    __________________________________________________________________________        Carbon                                                                              Ethylene-                                                                           Catalyst    Reaction                                                                             Reaction                                   Sample                                                                            dioxide                                                                             imine (Lewis acid)                                                                         Solvent                                                                            temperature                                                                          time 2-oxazolidone                         No. (l) (S.T.P.)                                                                        (g)   (mg)   (g)  (°C.)                                                                         (hour)                                                                             (g)                                   __________________________________________________________________________                           methylene                                                              iodine chloride                                               8   10    3     30     80   80     20   1.8                                                   copper tetrahy-                                                               iodide drofuran                                               9   5.5   3.2   80     30   80     73   0.9                                                          methylene                                                                     chloride                                               10  10    3     --     80   80     50   0.2                                   __________________________________________________________________________

EXAMPLE 11-16

The same procedure as that described in Example 1 was repeated exceptthat the procedure was carried out in a stainless steel high-pressuretube of about 50 ml under the conditions as shown below to obtain2-oxazolidone derivatives such as N-(β-cyanoethyl)-2-oxazolidone,3-acryloyl-2-oxazolidone and 3-phenyl-2-oxazolidone:

    __________________________________________________________________________         Carbon                                                                              Aziridine                                                                            Catalyst         Reaction                                                                             Reaction                                                                           2-oxazolidone                  Example                                                                            dioxide                                                                             compound                                                                             (Lewis acid)                                                                             Solvent                                                                             temperature                                                                          time derivative                     No.  (l) (S.T.P.)                                                                        (g)    (mg)       (g)   (°C.)                                                                         (hour)                                                                             (g)                            __________________________________________________________________________               N-(β-cyano-                    3-(β-cyano-                          ethyl)-                                                                              ferric                       ethyl)-2-                      11   3     ethylene-                                                                            chloride   n-heptane                                                                           70     24   oxazolidone                               imine  30         8                 1.1                                       1                                                                             N-(β-cyano-                                                                     antimony   chloroform        3-(βcyano-                           ethyl)-                             ethyl)-2-                                 ethylene-                           oxazolidone                               imine                                                              12   3     1      trichloride                                                                              10    70     30   1.3                                              30                                                                     N-(β-cyano-                                                                     alumium    o-dichloro-       3-(β-cyano-                          ethyl)-                             ethyl)-2-                                 ethylene-                           oxazolidone                               imine                                                              13   3     1      chloride   benzene                                                                             80     30   0.3                                              30         5                                                           N-β-cyano-   chloroform                                                                          80     24   3-(βcyano-                           ethyl)-                             ethyl)-2-                                 ethylene-                           oxazollicone                              imine                                                              14   3     1      --         5                 0.2                                       N-acryloyl-                                                                          iodine     dioxane           3-acryloyl-                    15   3     ethylene-                                                                            60         10    60     30   2-oxazolidone                             imine                               2.1                                       3                                                                             N-phenyl-                                                                            bromine    tetrahydro-       3-phenyl-                      16   2     ethylene-                                                                            60         furan 60     24   2-oxazolidone                             imine             10                1.2                                       3                                                                  __________________________________________________________________________

We claim:
 1. A process for preparing 2-oxazolidone compounds of theformula ##STR7## which comprises reacting carbon dioxide with anaziridine compound of the formula ##STR8## at a temperature of from 0°to 200° C., and a mol ratio of carbon dioxide to said aziridine compoundof from 0.1 to 1000, wherein R₁ is selected from the group consisting ofhydrogen, lower alkyl of 1 to 4 carbon atoms, phenyl and benzyl and R₂is selected from the group consisting of hydrogen, lower alkyl of 1 to 4carbon atoms, β-cyanoethyl, β-aminopropyl, α-hydroxyethyl,β-chloroethyl, phenyl, benzyl, and acyl selected from the groupconsisting of formyl, acetyl, propionyl, benzoyl, toluoyl, acryloyl andmethacryloyl.
 2. A process for preparing 2-oxazolidone compoundsaccording to claim 1, comprising reacting carbon dioxide with saidaziridine compound in the presence of a Lewis acid catalyst.
 3. Aprocess according to claim 2 wherein said Lewis acid is selected fromthe group consisting of halogens and halogenides of titanium, aluminium,manganese, copper, tin, antimony, iron, zinc, phosphorus and boron.
 4. Aprocess according to claim 3, wherein said halogens are chlorine,bromine and iodine and said halogenides are chlorides, bromides andiodides.
 5. A process according to claim 1, wherein said reaction isconducted in a solvent selected from the group consisting of saturatedparaffinic hydrocarbons, aromatic hydrocarbons, cycloparaffinichydrocarbons, alcohols, ethers, ketones, halogenated hydrocarbons,cyclic ethers, and amides.
 6. A process according to claim 1, whereinsaid molar ratio is 1 to
 100. 7. A process according to claim 1, whereinsaid temperature is 20°-120° C.